Metallizable trisazo dyestuffs



United States Patent METALLIZABLE TRISAZO DYESTUFFS Marcel Reding andWerner Bossard, Basel, Switzerland, assignors to J. R. Geigy A. G.,Basel, Switzerland, a Swiss firm I No Drawing. Application September 14,1953,

Serial No. 380,128

Claims priority, application Switzerland October 16, 1952 8 Claims. (Cl.260--173) The present invention concerns the production of new,metallisable trisazo dyestuffs, the coppered cellulose dyeings of whichhave very good fastness properties. They dye cellulose material by thedirect dyeing method in yellow-green to green shades which are notchanged much by the coppering process. Very pure yellow-green or greencoppered cellulose dyeings are obtained according to the composition ofthe dyestuif, some of which have such excellent fastness to Washing thatthey withstand repeated soap washings. The dyestuffs according to thisinvention supplement the group of fast, copperable trisazo dyestuffs ata point of the spectrum where at present there are not sutlicientdyestuffs to fulfill the high demands made upon them.

It has been found the type COOH acyl 1 .N=N H-CONH-BN==ND-N=N-E (I) canbe obtained, if a diazotised amino compound of the benzene series (A)containing a carboxyl group in the o-position to the diazo group, iscoupled with a new middle component of the composition:

which is more fully described below, diazotizing the amino azo dyestufiiso obtained and coupling the diazo compound in an acid medium with al-aminonaphthalene compound (D) coupling in the 4-position whichcontains a substituent suitable for the formation of the metal complexin the 2-position, in particular an alkoxy group. If desired, this canalso be further substituted by a carboxyl group with advantage. Theaminodisazo dyestutf so obtained is then diazotised and coupled in analkaline medium with a 2-acylamino-6-hydroxynaphthalene-8-sulphonic acid(E).

In these middle components of the above Formula II containing theradical B, each of I11, and n2 represents an integer of the value of 0or 1, X represents the direct carbon-to-carbon linkage or a CO-NH or angroup, one of Y1 and Ya represents hydrogen and the other represents anacyl-CH2-CO group, wherein acyl" means an alkoyl or a benzoyl radical.All the benzene rings in this formula as well as in all formulae derivedtherefrom can contain the non-ionogenic substituents usual in azodyestuffs, alkoxy groups. So that the trisazo dyestuffs according to thepresent invention which are distinguished particularly by their pureyellow-green to green shades, will be obtained, it is necessary that inone of the benzene rings in the Formula II the substituents according tothe definition, the position of which is not fixed, should be in themeta positions. The new middle components usable according to thepresent invention (corresponding to B) are monoprimary amino compoundswhich are derived from polynuclear, substantive diamino compounds of thediphenyl, diphenyl urea and bezanilide series having a sulphonic acidgroup standing in the o-position to an amino groupand wherein an aminogroup is acyloacetylated and a benzene ring is meta-substituted asdefined.

1.4 diaminobenzene-2-sulphonic acids, 4.4'-diaminodithat valuabletrisazo dyestuffs of for example, halogen, alkyl orphenyl-3-sulphonicacid, 4.4'-diaminodiphenyl urea-3-sulphonic acid and4-(4-arninobenzoylamino)-l-aminobenzene-Z-sulphonic acids for examplecan be used as starting materials for the production of such middlecomponents of the general (Formula II. They can be converted intomono-m-nitrobenzoylor mono-rn-nitrophenylcarbamyl derivatives accordingto known methods with m-nitrobenzoyl halides or m-nitrophenylisocyanates. The aqueous solution of their alkali salts is then treatedat 40-60 C. with diketene until the primary amino groups havedisappeared and the nitro groups are reduced to amino groups. In thismanner, in the process according to this invention, particularlyfavorable middle components are obtained which contain anacetoacetylamino group in the o-position to the sulphonic acid group. Itis also possible however, first to reduce the nitro group to the aminoof the alkali salts in the cold with diketene, in which process only theamino group not in the neighboring position to the sulphonic acid groupis; acetoacetylated. Thus in the process according to the presentinvention, further usable middle components of the Formula II having aprimary amino group in the neighboring position to the sulphonic acidgroup are obtained. Finally, also 3'-(p-nitrobenzoylorp-nitrophenylcarbamylamino)- 4-aminodiphenyl urea-3-sulphonic acids or4- [3'-(p-nitrobenzoylor p-nitrophenylcarbamylamino)-benzoylamino]-l-aminobenzene-Z-sulphonic acids can eitherfirst be reduced and then treated with diketene in the cold, or inreverse, first treated in the warm with diketene and then the nitrogroup can be reduced to the amino group. In this way also middlecomponents of the Formula II usable according to the present inventionare obtained. Because of their easier accessibility and their bettersuitability for the building up of the trisazo dyestuffs according tothe present invention, the dinuclear middle components of the Formula II(n2=O) are to be preferred to the polynuclear; Middle components of theFormula II which contain the radical SIOaH produce particularly valuabledyestuffs.

If diazotised Z-aminobenzene carboxylic acids are reacted in an alkalinemedium with compounds of the Formula II, the coupling occurs in theacyloacetyl radical and metallizable amino-monoazo dyestuffs areobtained which can be further diazotised.

As starting components, those usual in metallizable azo dyestuffs can beused, namely Z-aminobenzene-l-carboxylic acids. These compounds cancontain further substituents, e. g. halogen alkyl, alkoxy, carboxyl,sulphonic acid, sulphonic acid amide, sulphonic acid amide groupsorganically substituted at the nitrogen atom, alkyl sulphonyl,arylsulphonyl and acylamino groups.

2-alkoXy-1-aminonaphthalene compounds coupling in the 4-position can beused as the second. coupling components D, e. g. l-amino-Z-methoxyorethoXy-naphthalene, 1-am'ino-2-naphthyl-glycolic acid and derivativesthereofsulphonated in the 6- or 7-position of the naphthalene ring.l-amino-2-naphthyl-glycolic acid often has a favorable influence on thedrawing power of the trisazo dyestuffs according to the presentinvention, and is therefore, to be preferred.

The Z-acylamino-6-l1ydroxynaphthalene 8 sulphonic acids used as endcomponents E can contain as acyl radicals alkoyl radicals derived fromlower fatty acids which group and then treat the aqueous solution 9 i o4-chloro or methoxy or methyl-3-aminobenzoyl, 4-methshade is onlyslightly altered on after-treating the celoxyor ethoxybenzoyl radicals,further radicals of alilulose dyeings with agents givng off copper; onthe other cyclic or heterocyclic carboxylic acids as well as acyl handthe fastness to wet and light is considerably 1mradicals derived fromcarbonic acid such as carbamyl and proved. The coppering process can beperformed in carbalkoxy radicals, e. g. the dimethylcarbamyl or a aneutral to weakly acid medium in the dyebath or in a phenylcarbamylgroup or the carbethoxy, carbornethoxy, fresh bath with the usual coppersalts such as e. g. copthe carbomethoxy-ethoxy group. The final couplingis per acetate or copper sulphate. If desired, copper comadvantageouslyperformed in an alkaline medium in the pounds can be used which arestable to alkali such as presence of tertiary organic bases, e. g. inthe presence are obtained by reacting copper sulphate with sodium ofpyridine and homologues thereof. tartrate in a soda-alkaline bath.

The trisazo dyestulfs of the invention can also be de- The followingexamples illustrate the invention Withfined as corresponding to theformula out limiting it in any way. Where not otherwise stated, SOsH Y011 COOH acyl 1LN=N-(I3 H0 0 NHEB V-XON=N -N=N S O :11

l J z A NH-R wherein A represents an aromatic radical of the benzeneparts are given as parts by weight and the temperatures seriescontaining the earboxyl group in the o-position to are in degreesCentigrade. The relationship of parts the azo linkage, B stands for thegroup by weight to parts by volume is as that of kilogrammes SOSH V tolitres. .1 Example 1 21.6 parts of Z-aminobenzoic acid-S-sulphonic acidL amide are dissolved with 15 parts of concentrated hyeach of n and m isone of the numerals 0 and 1, each drochloric acid in 200 parts of waterand diazotised at of U and V represents an aromatic radical of the ben-10 with 6.9 parts of sodium nitrite. The resulting soluzene series, inone of which the bonds shown stand in tion is poured into a solution of41 parts of 5-(3'-acetothe m-position and in the other the bonds shownstand acetylaminobenzoylamino) 2 aminobenzene l sulin the p-position,both of which are free from carboxylic phonic acid in 400 parts of waterand 24 parts of sodiacid and sulphonic acid groups, X represents abridging um bicarbonate. On completion of the coupling the yelmemberselected from the group consisting of the direct low monoazo dyestuff issalted out and filtered off. The carbon-carbon linkage and the groups--CONH and filter cake is dissolved in 1000 parts of water and 6.9NHCONH, acyl represents a member selected parts of sodium nitrite areadded. A yellow diazo susfrom the group consisting of alkoyl and benzoylradipension is obtained by the dropwise addition of parts cals, Yrepresents a member selectedfrorn the group of concentrated hydrochloricacid at lO-15, which is consisting of alkoxy and OCH2COOH groups, one Z40 made weakly acid to Congo red after stirring for 4 hours representshydrogen and the other Z represents a memw1th 5 parts of sodiumcarbonate. It was then coupled ber selected from the group consisting ofhydrogen and with a solution of 21.7 parts of 1-amino-2-naphthylglythesulphonic acid group and R represents a carboxyhc colic acid and 20parts of sodium acetate. To accelerate acid acyl radical bound directlyto the adjacent NH- the reaction, 4 parts of sodium carbonate are addedto group by the CO group. keep the reaction slightly acid. The disazodyestuff These dyestuffs include products of the formulae formed isdissolved with 5 parts of caustic soda, mixed wherein A, acyl, X, Y, Zand R have the aforesaid sigwith 400 parts of sodium chloride, parts ofconcennlficances, and represents an aromatic radical of the tratedhydrochloric acid and diazotized with 8.2 parts benzene series in whichthe bonds shown stand in mof sodium nitrite at 20. On completion of thediazoposition of said aromatic radical and which is free from Ntization, the diazo compound is filtered off and washed. carboxylic ac1dand sulphonic acid groups. It is then coupled with 34.3 parts of2-benzoylam-iuo-6- In the form of their alkali salts, the new trisazodyehydroxynaphthalene-ii-sulphonic acid in 200 parts, of wa stuffsdissolve in hot water with a green color and they ter in the presence ofparts of pyridine and 20 parts dye cellulose fibers direct from adyebath containing of sodium carbonate. Glaubers salts in yellow-greento green shades. The The green trisazo dyestuff of the formula:

COOH

is precipitated with a little sodium chloride, filtered .off and freedfrom adhering impurities by washing.

It is a dark powder which dissolves in water with a, green and inconcentrated sulphuric acid with an olive green color. It dyes fibresfrom natural or regenerated cellulose in vivid yellowish-green shades.The dyeings are made fast to light, washing and acid by after-treatmentwith copper salts.

If in this example 13.7 parts of Z-aminobenzoic acid, 19.4 parts of 4-or 5-acetylamino-2-aminobenzoic acid, 21 parts of Z-amino-lcarboxyphenyl-4- Or-S-carbamic acid methyl ester, 22.4 parts ofZ-amino-l-carboxyphenyl-4- or -5-carbamic acid ethyl ester, 25.4 partsof 2-amino-1-carboxyphenyl-4- or -5-carbamic acid methoxyethyl ester,26.8 parts of Z-amino-l-carboxyphenyl-4- or -5-carbamic acid ethoxyethylester, 25.2 parts of 5- succinylamino-Z-aminobenzoic acid, 18.1 parts of2-aminobenzene-1.4- or 1.5-dicarboxylic acid, 21.7 parts of 2-aminobenzoic acid-4- or -5-sulphonic acid, 23 parts of 2 aminobenzoicacid5-sulphonic acid methylamide, 24.4 parts of Z-aminobenzoicacid-S-sulphonic acid dimethyl amide, 2.6 parts of 2-arninobenzoicacid-5-sulphonic acid- B-oxethyl amide, 21.5 parts of 4- orS-methylsulphonyl- 2-aminobenzoic acid, 17.2 parts of 2-amino-4- or -5-chlorobenzoic acid, 20.6 parts of 2-amino-4.6-dichlorobenzoic acid or15.1 parts of 2-amino-4-methyl'oenzoic acid are used instead of 21.6parts of 2-aminobenzoic acid-S-sulphonic acid amide, analogous greentrisazo dyestuffs are obtained which have similar properties.

Example 2 21.6 parts of Z-aminobenzoic acid-S-sulphonic acid amide aredissolved at 50 with 7.5 parts of sodium carbonate in 500 parts ofWater. 6.9 parts of sodium nitrite are added and the solution is pouredat 0 onto 30 parts of concentrated hydrochloric acid. The diazoniumsolution is poured into 40.6 parts of3'-acetoacetylamino,-4-amino-1.l'-diphenyl urea-3-sulphonic acid in 400parts of water and 24 parts of sodium bicarbonate. The yellow monoazodyesturf is isolated, dissolved in 1000 parts of Water and diazotized at-15 with 6.9 parts of sodium nitrite and 40 parts of concentratedhydrochloric acid. The diazonium compound neutralized with 4 parts ofsodium carbonate is poured at O5 into a solution of 21.7 parts of1-amino-2-naphthyl glycolic acid to which has been added parts of sodiumacetate.

| COCHs COOH 80:13:

The reaction of the coupling is kept weakly acid by the addition of 5parts of sodium carbonate. The violet disazo dyestuff dissolves with 5parts of caustic soda and is further diazotized as described inExample 1. The isolated diazonium compound can be coupled with 34.8parts of 6-hydroxynaphthyl-(2)-carbamic acid-methoxyethylester-S-sulphonic acid in 200 parts of water with the addition of 20parts of sodium carbonate and 150 parts of pyridine to form the greentrisazo dyestuff of the formula:

COOH

l COCH:

It is a dark powder which dissolves in water with a green and inconcentrated sulphuric acid with an olive green color. It dyes cotton,rayon, viscose, hemp and jute in green shades. After treatment withcopper compounds according to one of the usual methods, the dyeings havevery good fastness properties.

If in this example the 21.6 parts of 2-aminobenzoic acid-S-sulphonicacid amide are replaced by 13.7 parts of Z-aminobenzoic acid, 19.4 partsof 4- or S-acetylamino-2-aminobenzoic acid, 21 parts of2-amino-1-carboxy- 5 phenyl-4- or -5-carbamic acid-methylester, 22.4parts of 2amino-1-carboxyphenyl-4- or -5-carbamic acid-ethylester or25.4 parts of 2-amino-1-carboxyphenyl-4- or -5- carbamic acidmethoxyethyl ester or 26.8 parts of 2- amino-1-carboxyphenyl-4- or-5-carbamic acid ethoxyethyl ester or 25.2 parts of5-succinylamino-2-aminobenzoic acid or 18.1 parts of 2-aminobenzene-1,4-or -1.5-dicarboxylic acid, 21.7 parts of Z-aminobenzoic acid-4- or-5-sulphonic acid or 23 parts of Z-aminobenzoic acid-5- sulphonic acidmethylamide or 24.4 parts of Z-aminobenzoic acid-5-sulphonic aciddimethylamide or 26 parts of 2-aminobenzoic acid-S-sulphonicacid-,B-oxethylamide or 21.5 parts of 4- or5-methylsulphonyl-2-aminobenzoic acid or 17.2 parts of 2-amino-4- or-5-chlorbenzoic acid or 20.6 parts of 2-a1nino-4.6-dichlorobenzoic acidor 15.1 parts of 2-amino-4-methylbenzoic acid, similar green trisazodyestuffs with similar properties are obtained.

Example 3 19.4 parts of 2-arnino-5-acetylaminobenzoic acid are dissolvedat in 120 parts of water with 6.4 parts of sodium carbonate, mixed with6.9 parts of sodium nitrite and cooled With ice to 0. 30 parts ofconcentrated hydrochloric acid are quickly added and the diazosuspension is coupled with 39.1 parts of5-(3'-aminobenzoylamino)-2-acetoacetylarninobenzene-l-sulphonic acid and30 parts of sodium carbonate in 400 parts of water. The monoazo dyestuifis isolated and diazotized as described in Example 1, and theneutralized diazonium compound is poured into the solution of 21.7 partsof l-amino-2- naphthylglycolic acid and 20 parts of sodium acetate in660 parts of water. The Whole is stirred overnight, then the disazodyestuff which forms is dissolved with 5 parts of caustic soda,converted into the sodium salt with 400 parts of sodium chloride anddiazotized at 25 with parts of hydrochloric acid and 8.2 parts of sodiumnitrite. The diazonium compound formed is filtered off and coupled with28.1 parts of 2-acetylamino-fi-hydroxynaphthalene-8-sulphonic acid in200 parts of water, 150 parts of pyridine and 20 parts of sodiumcarbonate. The trisazo dyestuif of the formula:

COOH

HO 0 (301120 OH SOaH / NH0 0 0 CHzCHrOCHI and otherwise the proceduredescribed above is followed, similar dyestuffs with similar propertiesare obtained.

Example 4 I 13.7 parts of Z-aminobenzoic acid are diazotized and coupledwith 40.6 parts of 3'-amino-4-acetoacetylaminor 7 l.ldiphenylurea-3-sulphonic acid in 400 parts of water with the addition of 24parts of sodium bicarbonate. The yellow monoazo dyestufr is isolated,dissolved and diazotized as described in Example 3. The neutralizeddiazcnium compound is poured into a solution of 29.7 parts of1-amino-2-naphthylglycolic acid-6-sulphonic acid and 20 parts of sodiumacetate in 400 parts of Water. The violet disazo dyestuti is diazotizedwith 60 parts of concentrated hydrochloric acid and 8.2 parts of sodiumnitrite in the presence of sodium chloride, filtered and the diazoniumcompound is coupled with a soda alkaline solution of 34.3 parts ofZ-benzoylamino-6-hydroxynaph- OOOH thalene-S-sulphonic acid in 200 partsof water and 150 parlts of pyridine to form the trisazo dyestufi of theforrnu a:

l on;

stirring for 4 hours, the neutralized suspension is poured into asolution of 29.7 parts of l-amino-2-naphthylglycolic acid-7-sulphonicacid to which has been added 20 parts of sodium acetate. The disazodyestulf obtained is violet and, with the addition of 400 parts ofsodium chloride, is further diazotized with 8.2 parts of sodium nitriteand 60 parts of concentrated hydrochloric acid. It is filtered off andfinally coupled with an aqueous solution of 34.3 parts of2-benzoylarninc-6hydroxynaphthalene-8- sulphonic acid, 20 parts ofsodium carbonate and 150 parts of pyridine. The green trisazo dyestuifof the formu 2::

HOOCCHzO SOaH NH-C 00 COOH SOsH The dried dyestufi is a dark powderwhich dissolves in water and in concentrated sulphuric acid with a greencolor. It dyes natural and regenerated cellulose green. Onafter-treatment with copper salts, the fastness of the dyeings to light,washing and acid is increased.

Similar dyestuffs with similar properties are obtained it the 34.3 partsof 2-benzoylamino--hydroxynaphthalene-S-sulphcnic acid are replaced by35.8 parts of 2- (3 aminobenzoylamino) 6 hydroxynaphthalene-8-sulphonicacid or 28.1 parts of 2-acetylamino-6-hydroxynaphthalene-8-sulphonicacid or 35.8 parts of2-(4-aminobenzoylamino)-6-hydroxynaphthalene-8-sulphonic acid or 39.3parts of 2-(4-chloro-3-aminobenzoylamino)-6-hydroxynaphthalene-8-sulphonic acid or 37.9 parts of 2- f Example 46.7parts of 4'-(3"-acetoacctylaminobenzoylamino)-4-aminodiphenyl3-sulphonic acid are dissolved in 400 parts of water and 24parts of sodium bicarbonate are added. The diazonium compound made upfrom 26 parts of 2- aminobenzoic acid-S-sulphonic acid-,l-3-ethanolamidewhich has been prepared. in the usual Way is added to this solution. Theyellow monoazo dyestuff obtained is precipitated with sodium chlorideand filtered off. The filter cakes are dissolved in 1000 parts of waterand diazotized according to the method described in Example 1. After Iphenyl-3-sulphonic acid are used, or if instead of the 26 parts of2-aminobenzoic acid-S-sulphonic acid-fl-ethanolamide equivalent parts ofanother of the Z-arninocarboxybenzene compounds listed in Example 1 areused, analogous dyestuffs With similar properties are obtained.

Example 6 21 parts of Z-amino-5-carbomethoxyaminobenzene-1- carboxylicacid are dissolved at in 180 parts of water with 4.1 parts of causticsoda, mixed with 30 parts of concentrated hydrochloric acid anddiazotised by the addition of 6.9 parts of sodium nitrite. The diazoniumcompound is coupled with 52.4 parts ofS-[4-(3-acetoacetylamino-4"-rnethylbenzoylamino)-benzoylamino]-2-aminobenzene-l-sulphonicacid in 600 parts of water and 30 parts of sodium carbonate to form ayellow monoazo dyestult. After isolating this dyestuff, it is dissolvedin 1000 parts of Water and further diazotized with 6.9 parts of sodiumnitrite and parts of concentrated hydrochloric acid. The isolateddiazonium compound is coupled with 25.3 parts ofl-amino-2-methoxynaphthalene--sulphonic acid in 200 parts of water inthe presence of 20 parts of sodium acetate to form the violet disazodyestuff. The reaction is made weakly acid with 5 parts of sodiumcarbonate to accelerate the reaction. The disazo dyestufi is diazotizedaccording to the method given in Example 1. Finally, the isolateddiazonium compound is coupled with a solution of 28.] parts of2-acetylamino-6-hydroxynaphthalene-S-sulphonic acid in 200 parts ofWater, 20 parts of sodium carbonate and parts of pyridine to form thetrisazo dyestufl of the formula:

so 311 I o CH3 on coon Olly-QC O-NHQC O-NHC \T=N *=N soin CmOcdNHONN-oH-oO-NH v COCH so=n rin-oo-on.

It is isolated with a little sodium chloride and when dry, it is a darkpowder which dissolves in water with a green and in concentratedsulphuric acid with a yellowish-green color. The dyeings on cellulosefibres are green and on after-treating with copper salts, are fast tolight, washing and acid.

If instead of 52.4 parts of -[4-(3"-acetoacetylamino-4"-methylbenzoylamino) benzoylamino] 2 aminobenzene-l-sulphonic acid, 51parts of 5-[4'-(3"-acetoacety1- aminobenzoylamino)-benzoylamino] 2aminobenzenel-sulphonic acid or 52.4 parts of5-[3'-(3"-acetoacetylamino-4-methylbenzoylarnino -benzoylamino-2-aminobenzene-l-sulphonic acid or 52.5 parts of4'-(3-acetoacetylarninobenzoylamino)-4-amino 1.1 diphenyl urea-3-sulphonic acid or 52.5 parts of 5'[4'-(3"-acetoacetylaminophenylureido)-benzoylamino}-2-aminobenzene l sulphonic acid, 53.9parts of 5-[4-(3-acetoacetylamino- 4-methylphenylureido) benzoylamino] 2aminobenzene-l-sulphonic acid or 45.3 parts of5-(3-aminobenzoylamino)-2-benzoylacetylaminobenzene 1 sulphonic acid or46.7 parts of 5-(4-amino-3'-methylbenzoylamino)-2-benzoylacetylarninobenzene-l-sulphonic acid are used,

obtained.

Example 7 13.7 parts of 2-aminobenzoic acid are diazotized as describedin Example 4 and coupled with a soda alkaline solution of 40.6 parts of3'-amino-4-acetoacetylarnino- 1.1-dipheny1 urea-3-sulphonic acid. Theprecipitated monoazo dyestuif is filtered off, dissolved in 1000 partsof water and diazotized at 10--15 with 6.9 parts of sodium nitrite andparts of concentrated hydrochloric acid. After 4 hours, the diazoniumcompound is made weakly acid to Congo red with 5 parts of sodiumcarbonate and added to a solution of 21.7 parts ofl-amino-Z-naphthaleneglycolic acid in 600 parts of water with theaddition of 20 parts of sodium acetate. The whole is stirred overnightand then the violet disazo dyestufi? which forms is 5 further diazotizedthe next day. The dyestuff is isolated and coupled with 31.3 parts of2-carbethoxyamino-6- hydroxynaphthalene-S-sulphonic acid in 200 parts ofwater, 150 parts of pyridine and 20 parts of sodium car- OCHZCOOH groupsone Z represents hydrogen and bonate. After isolating and washing freefrom impurities, the trisazo dyestuif of the formula:

GOOH

OzH B:

when dry is a dark powder which dissolves in Water with a green and inconcentrated sulphuric acid with a brown color. Natural or regeneratedcellulose fibres are dyed green. are made fast to light, washing andacid.

C O OH acyl 10 water and 2 parts of soda.

If in this example the 13.7 parts of Z-aminobenzoic acid are replaced bythe corresponding number .of parts of another of the Z-aminobenzoicacids listed in Example 2, similar green dyestuffs with similarproperties are obtame Example 8 15 in a fresh bath with 2 parts ofcrystallised copper sulphate in 2000 parts of water and 2 parts of 30%acetic acid for half an hour. The goods are rinsed and dried in theusual way. The cotton is dyed in green shades which have excellentfastness properties.

What we claim is:

l. A trisazo dyestuff of the formula wherein A represents an aromaticradical of the benzene series containing the carboxyl group in the0-position to the azo linkage, B stands for the group sOsH each of n andm is one of the numerals 0 and 1, each zene series, in one of which thebonds shown stand in the m-position and in the other the bonds shownstand in the p-position, both of which are free from carboxylic acid andsulphonic acid groups, X represents a bridging member selected from thegroup consist- .ing of the direct carbon-carbon linkage and the groups-CO-NH and -NH-CONH, acyl represents a member selected from the groupconsisting of alkoyl and benzoyl radicals, Y represents a memberselected from the group consisting of alkoxy and the other Z representsa member selected from the OCHzCOOH OH group consisting of hydrogen andthe sulphonic acid group and R represents a carboxylic acid acyl radicalbound directly to the adjacent --NH group by the On after-treating withcopper salts, the dyeings -CO- group.

2. A trisazo dyestuff of the formula SOaH wherein A represents anaromatic radical of the benzene series containing the carboxyl group inthe 0-position to the azo linkage, V represents an aromatic radical ofthe benzene series in which the bonds shown stand in m-position of saidaromatic radical and which is free from carboxylic acid and sulphonicacid groups, X represents a bridging member selected from the groupconsisting of the direct carbon-carbon linkage and the groups -CONH- andNHCO-NH-, acyl represents a member selected from the group consist ingof alkoyl and benzoyl radicals, Y represents a member selected from thegroup consisting of alkoxy and -OCH2COOH groups, one Z representshydrogen and the other Z represents a member selected from the groupconsisting of hydrogen and the sulphonic acid group and R represents acarboxylic acid acyl radical bound directly to the adjacent --NI-I-groupby the -CO- group.

3. A trisazo dyestufi': of the formula SOaH COOH COOH SOsH COCH:

( OOH $0311 COCH:

CODE 80311 COCH;

(\IOOH References Cited in the file of this patentwherein A representsan aromatic radical of the benzene series containing the carboxyl groupin the 0-position to the azo linkage, V represents an aromatic radicalof the benzene series in which the bonds shown stand in m-position ofsaid aromatic radical and which is free from carboxylic acid andsulphonic acid groups, X represents a bridging member selected from thegroup consisting of the direct carbon-carbon linkage and the groupsCO-NH and NHCONH, acyl represents a member selected from the groupconsisting of alkoyl and benzoyl radicals, Y represents a memoerselected from the group consisting of alkoxy and OCH2COOH groups, one Zrepresents hydrogen and the other Z represents a member selected fromthe group consisting of hydrogen and the sulphonic acid group and Rrepresents a carboxylic acid acyl radical bound directly to the adjacentNH- group by the CO group.

NHR

4. The trisazo dyestuff of the formula I hagsngem NHC 0-CH1 5. Thetrisazo dyestufi of the formula:

NHC0CH1 6. The trisazo dyestutf of the formula:

7. The trisazo dyestufi of the formula:

8. The trisazo dyestuff of the formula:

HOOCCHzO OH -SO3H 1 SOaH r IH-O 0'0 UNITED STATES PATENTS 1,594,865Zitscher Aug. 3, 1926 2,115,412 Dahlen et al. -Apr. 26, 1938 2,515,546Bossard et al. July 18, 1950 FOREIGN PATENTS 367,675 Great Britain Feb.25, 1932

1. A TRISAZO DYESTUFF OF THE FORMULA